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Title: Photoelectron Spectroscopy of Adiabatically Bound Valence Anions of Rare Tautomers of the Nucleic Acid Bases

Abstract

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Anionic states of nucleic acid bases (NABs) are involved in DNA damage by low-energy electrons and in charge transfer through DNA. Previous gas phase studies of free, unsolvated NAB parent anions probed mostly dipole-bound states, which are not present in condensed phase environments. Recently, we demonstrated that very rare tautomers of uracil (U), cytosine (C), adenine (A), and guanine (G), which are obtained from canonical tautomers through N-to-C proton transfers, support valence anionic states. Here we report the photoelectron spectrum of the final member of the NABs series: the valence state of the thymine (T) anion. Additionally, we summarized the work of all five NABs. All of the newfound anionic tautomers of the NABs may be formed via dissociative electron attachment followed by hydrogen atom reattachment to a carbon atom. Furthermore, these unusual tautomers may affect the structure and properties of DNA and RNA exposed to low-energy electrons. The new valence states observed here, unlike dipole bound states, could existmore » in condensed phases and may be relevant to radiobiological damage.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
926953
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics, 127(17):Art. 174309
Additional Journal Information:
Journal Name: Journal of Chemical Physics, 127(17):Art. 174309
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Li, Xiang, Bowen, Kit H, Haranczyk, Maciej, Bachorz, Rafal A, Mazurkiewicz, Kamil, Rak, Janusz, and Gutowski, Maciej S. Photoelectron Spectroscopy of Adiabatically Bound Valence Anions of Rare Tautomers of the Nucleic Acid Bases. United States: N. p., 2007. Web. doi:10.1063/1.2795719.
Li, Xiang, Bowen, Kit H, Haranczyk, Maciej, Bachorz, Rafal A, Mazurkiewicz, Kamil, Rak, Janusz, & Gutowski, Maciej S. Photoelectron Spectroscopy of Adiabatically Bound Valence Anions of Rare Tautomers of the Nucleic Acid Bases. United States. https://doi.org/10.1063/1.2795719
Li, Xiang, Bowen, Kit H, Haranczyk, Maciej, Bachorz, Rafal A, Mazurkiewicz, Kamil, Rak, Janusz, and Gutowski, Maciej S. Wed . "Photoelectron Spectroscopy of Adiabatically Bound Valence Anions of Rare Tautomers of the Nucleic Acid Bases". United States. https://doi.org/10.1063/1.2795719.
@article{osti_926953,
title = {Photoelectron Spectroscopy of Adiabatically Bound Valence Anions of Rare Tautomers of the Nucleic Acid Bases},
author = {Li, Xiang and Bowen, Kit H and Haranczyk, Maciej and Bachorz, Rafal A and Mazurkiewicz, Kamil and Rak, Janusz and Gutowski, Maciej S},
abstractNote = {The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Anionic states of nucleic acid bases (NABs) are involved in DNA damage by low-energy electrons and in charge transfer through DNA. Previous gas phase studies of free, unsolvated NAB parent anions probed mostly dipole-bound states, which are not present in condensed phase environments. Recently, we demonstrated that very rare tautomers of uracil (U), cytosine (C), adenine (A), and guanine (G), which are obtained from canonical tautomers through N-to-C proton transfers, support valence anionic states. Here we report the photoelectron spectrum of the final member of the NABs series: the valence state of the thymine (T) anion. Additionally, we summarized the work of all five NABs. All of the newfound anionic tautomers of the NABs may be formed via dissociative electron attachment followed by hydrogen atom reattachment to a carbon atom. Furthermore, these unusual tautomers may affect the structure and properties of DNA and RNA exposed to low-energy electrons. The new valence states observed here, unlike dipole bound states, could exist in condensed phases and may be relevant to radiobiological damage.},
doi = {10.1063/1.2795719},
url = {https://www.osti.gov/biblio/926953}, journal = {Journal of Chemical Physics, 127(17):Art. 174309},
number = ,
volume = ,
place = {United States},
year = {2007},
month = {11}
}